U.S. patent number 7,547,808 [Application Number 11/912,895] was granted by the patent office on 2009-06-16 for process for producing aldehyde with 2-position branched long-chain alkyl.
This patent grant is currently assigned to Idemitsu Kosan Co., Ltd.. Invention is credited to Yoshio Ikeda, Takashi Kashiwamura, Haruhito Sato.
United States Patent |
7,547,808 |
Sato , et al. |
June 16, 2009 |
Process for producing aldehyde with 2-position branched long-chain
alkyl
Abstract
To provide a process capable of producing an aldehyde with a
2-position branched long-chain alkyl with high yield and high
selectivity. The process for producing an aldehyde with a
2-position branched long-chain alkyl represented by the following
general formula (2) contains: using a 2-position branched epoxide
represented by the following general formula (1) as a raw material;
and subjecting the epoxide to acid rearrangement reaction with a
polyacid of a metallic oxoacid as a catalyst. In the formulae, n
represents an integer of from 5 to 17. ##STR00001##
Inventors: |
Sato; Haruhito (Chiba,
JP), Kashiwamura; Takashi (Chiba, JP),
Ikeda; Yoshio (Chiba, JP) |
Assignee: |
Idemitsu Kosan Co., Ltd.
(Tokyo, JP)
|
Family
ID: |
37683277 |
Appl.
No.: |
11/912,895 |
Filed: |
July 21, 2006 |
PCT
Filed: |
July 21, 2006 |
PCT No.: |
PCT/JP2006/314529 |
371(c)(1),(2),(4) Date: |
October 29, 2007 |
PCT
Pub. No.: |
WO2007/013379 |
PCT
Pub. Date: |
February 01, 2007 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20090076311 A1 |
Mar 19, 2009 |
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Foreign Application Priority Data
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Jul 25, 2005 [JP] |
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2005-214678 |
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Current U.S.
Class: |
568/483 |
Current CPC
Class: |
C07C
45/58 (20130101); C07C 45/82 (20130101); C07C
47/02 (20130101); C07C 45/58 (20130101); C07C
47/02 (20130101); C07C 45/82 (20130101); C07C
47/02 (20130101) |
Current International
Class: |
C07C
45/55 (20060101) |
Field of
Search: |
;568/483 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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03-090042 |
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Apr 1991 |
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JP |
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2004-256404 |
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Sep 2004 |
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JP |
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2004-331561 |
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Nov 2004 |
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JP |
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Other References
Badger, Alison M. et al., "Antiarthritic and Suppressor Cell
Inducing Activity of Azaspiranes: Structure-Function Relationships
of a Novel Class of Immunomodulatory Agents", J. Med. Chem., vol.
33, pp. 2963-2970, 1990. cited by other.
|
Primary Examiner: Witherspoon; Sikarl A
Attorney, Agent or Firm: Oblon, Spivak, McClelland, Maier
& Neustadt, P.C.
Claims
The invention claimed is:
1. A process for producing an aldehyde with a 2-position branched
long-chain alkyl represented by the following general formula (2)
comprising: using a 2-position branched epoxide represented by the
following general formula (1) as a raw material; and subjecting the
epoxide to acid rearrangement reaction with a polyacid of a
metallic oxoacid as a catalyst ##STR00005## (In the formulae, n
represents an integer of from 5 to 17).
2. The process for producing an aldehyde with a 2-position branched
long-chain alkyl as described in claim 1, wherein the 2-position
branched epoxide is an epoxidized product of a vinylidene olefin
obtained by dimerizing an .alpha.-olefin in the presence of a
metallocene complex catalyst.
3. The process for producing an aldehyde with a 2-position branched
long-chain alkyl as described in claim 1 or 2, wherein in the
general formulae (1) and (2), n represents an integer of from 7 to
9.
4. The process for producing an aldehyde with a 2-position branched
long-chain alkyl as described in one of claims 1 to 3, wherein the
polyacid of a metallic oxoacid is a polyacid containing tungstic
acid, molybdic acid or vanadic acid.
5. The process for producing an aldehyde with a 2-position branched
long-chain alkyl as described in claim 4, wherein the polyacid
containing tungstic acid, molybdic acid or vanadic acid is an
isopolyacid that is a polyacid of tungstic acid, molybdic acid or
vanadic acid, or a heteropolyacid that is a polyacid of tungstic
acid, molybdic acid or vanadic acid with phosphoric acid, silicic
acid or boric acid.
Description
TECHNICAL FIELD
The present invention relates to a process for producing an
aldehyde with a 2-position branched long-chain alkyl suitable for
an intermediate raw material used in production of a branched
alcohol, a branched fatty acid, an aliphatic amine and the like, a
resin raw material, such as 1,3-alkanediol and a bisphenol
derivative, and a raw material of a functional chemical utilizing a
Schiff base and the like.
BACKGROUND ART
A process for industrially producing a 2-position branched alcohol
(such as 2-octyl-1-dodecanol) by applying so-called Guerbet
reaction to a higher alcohol (such as 1-decanol) has been
conventionally known. However, only one report has been made for a
technique for producing a 2-position branched aldehyde (see Patent
Document 1). According to Patent Document 1, in the case where a
branched saturated aldehyde is produced by utilizing Guerbet
reaction, a branched alcohol and a branched unsaturated aldehyde
are present as mixtures, and thus it is expected that it is
difficult to produce a branched saturated aldehyde with high
purity. Patent Document 1 disclosed in Example 2 that the amount of
a hydrogenation catalyst is necessarily added in an amount of 7% by
mass for improving the yield of the branched aldehyde, but when the
ratio of the hydrogenation catalyst is decreased, such a problem
and the like arise in that a branched alcohol is produced as the
major product.
An aldehyde with a 2-position branched long-chain alkyl can be
produced through dimerization of a higher alcohol utilizing Guerbet
reaction, but the production process is not practical since the
activity per unit catalyst is significantly low.
Acid rearrangement reaction of a 1,2-epoxide of an .alpha.-olefin
provides various rearrangement products (which include aldehydes,
and also include ketones and unsaturated alcohols), and thus a
1,2-epoxide is utilized only for production of a 1,2-diol through
hydration reaction or production of a polyester polyol through
addition reaction with a dibasic carboxylic acid. It has been
reported that acid rearrangement of a 1,2-epoxide in a 1,4-dioxane
solvent provides a linear aldehyde (see, for example, Patent
Document 2). However, an aldehyde with a 2-position branched
long-chain alkyl cannot be produced by the production method using
an epoxide of an .alpha.-olefin.
Patent Document 1: U.S. Pat. No. 3,558,716
Patent Document 2: JP-A-2004-256404
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
The present invention has been made under the aforementioned
circumstances, and an object thereof is to provide a method capable
of producing an aldehyde with a 2-position branched long-chain
alkyl with high yield and high selectivity.
Means for Solving the Problems
As a result of earnest investigations made by the present
inventors, it has been found that by subjecting a 2-position
branched epoxide to acid rearrangement reaction using a polyacid of
a metallic oxoacid as a catalyst, an aldehyde with a 2-position
branched long-chain alkyl can be produced with high yield and high
selectivity, and the aldehyde with a 2-position branched long-chain
alkyl as a target product can be obtained at a high concentration
with a considerably high activity per unit catalyst, whereby such
operations as separation of the catalyst and purification can be
simplified. The invention has been completed based on the
findings.
The invention provides a process for producing an aldehyde with a
2-position branched long-chain alkyl shown below.
1. A process for producing an aldehyde with a 2-position branched
long-chain alkyl represented by the following general formula (2)
containing: using a 2-position branched epoxide represented by the
following general formula (1) as a raw material; and subjecting the
epoxide to acid rearrangement reaction with a polyacid of a
metallic oxoacid as a catalyst.
##STR00002## (In the Formulae, N Represents an Integer of from 5 to
17.)
2. The process for producing an aldehyde with a 2-position branched
long-chain alkyl as described in the item 1, wherein the 2-position
branched epoxide is an epoxidized product of a vinylidene olefin
obtained by dimerizing an .alpha.-olefin in the presence of a
metallocene complex catalyst.
3. The process for producing an aldehyde with a 2-position branched
long-chain alkyl as described in the item 1 or 2, wherein in the
general formulae (1) and (2), n represents an integer of from 7 to
9.
4. The process for producing an aldehyde with a 2-position branched
long-chain alkyl as described in one of the items 1 to 3, wherein
the polyacid of a metallic oxoacid is a polyacid containing
tungstic acid, molybdic acid or vanadic acid.
5. The process for producing an aldehyde with a 2-position branched
long-chain alkyl as described in the item 4, wherein the polyacid
containing tungstic acid, molybdic acid or vanadic acid is an
isopolyacid that is a polyacid of tungstic acid, molybdic acid or
vanadic acid, or a heteropolyacid that is a polyacid of tungstic
acid, molybdic acid or vanadic acid with phosphoric acid, silicic
acid or boric acid.
Advantage of the Invention
In the present invention, by subjecting a 2-position branched
epoxide to acid rearrangement reaction using a polyacid of a
metallic oxoacid as a catalyst, an aldehyde with a 2-position
branched long-chain alkyl can be produced with high yield and high
selectivity, and the aldehyde with a 2-position branched long-chain
alkyl as a target product can be obtained at a high concentration
with a considerably high activity per unit catalyst, whereby such
operations as separation of the catalyst and purification can be
simplified.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 The figure shows a .sup.1H-NMR spectrum of
2-octyl-1-dodecanal obtained in Example 1.
FIG. 2 The figure shows a .sup.13C-NMR spectrum of
2-octyl-1-dodecanal obtained in Example 1.
FIG. 3 The figure shows a homonuclear shift correlation (2D-COSY)
spectrum of 2-octyl-1-dodecanal obtained in Example 1.
BEST MODE FOR CARRYING OUT THE INVENTION
The 2-position branched epoxide represented by the general formula
(1) used as a raw material in the present invention can be
obtained, for example, by epoxidizing a vinylidene olefin (general
formula (4)) obtained by dimerizing an .alpha.-olefin (general
formula (3)) in the presence of a metallocene complex catalyst, as
shown by the following reaction pathway. By using the 2-position
branched epoxide (general formula (1)) as a raw material, the
epoxide is subjected to acid rearrangement reaction using a
polyacid of a metallic oxoacid, whereby the aldehyde with a
2-position branched long-chain alkyl (general formula (2)) is
produced.
##STR00003## (In the Formulae, N Represents an Integer of from 5 to
17, and Preferably from 7 to 9.)
In the acid rearrangement reaction, a long-chain alkyl 2-position
branched unsaturated alcohol represented by the following general
formula (i), a long-chain alkyl 2-position branched 1,2-diol
represented by the following general formula (ii), and an epoxide
dimer represented by the following general formula (iii) are formed
as by-products.
##STR00004## (In the Formulae, N has the Same Meaning as
Above.)
Examples of the metallocene complex catalyst used for dimerization
of the .alpha.-olefin include a catalyst containing a metallocene
complex and an organoaluminum compound, and a catalyst containing a
metallocene complex and a borate (an ionization agent of the
complex). A transition metal complex of Group 4 of the Periodic
Table having a conjugated 5-membered carbocyclic structure as a
ligand is used as the metallocene complex, and alkylaluminoxane or
a group of compounds having an alkyl group and metallic aluminum
bonded directly, such as trialkyl aluminum, is used as the
organoaluminum compound.
Examples of the .alpha.-olefin represented by the general formula
(3) include 1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene and 1-eicocene.
The metallocene complex includes a complex of a metal of Group 4 of
the Periodic Table having a conjugated 5-membered carbocyclic
structure, such as zirconocene dichloride,
bis(dimethylcyclopentadienyl) zirconium dichloride,
bis(indenyl)zirconium dichloride and
bis(tetrahydroindenyl)zirconium dichloride, a metallic complex
obtained by replacing zirconium in the metallic complex with
titanium or hafnium, and a metallic complex obtained by replacing
the chloride thereof with an alkyl group, a 1,3-diketone, a
.beta.-ketoester or trifluoromethane sulfonate.
Examples of the organoaluminum compound include alkylaluminoxane,
such as methylaluminoxane and isobutylaluminoxane, and an
alkylaluminum compound, such as triethylaluminum,
triisobutylaluminum and trioctylaluminum.
Examples of the borate include a dimethylanilinium salt of
tetrakis(pentafluorophenyl)borate, trityl
tetrakis(pentafluorophenyl)borate, trimethylammonium
tetrakis(pentafluorophenyl)borate, benzylpyridinium
tetrakis(pentafluorophenyl)borate and trityl tetraphenylborate.
The dimerization reaction of the .alpha.-olefin can be carried out,
for example, in such a manner that the catalyst and the
.alpha.-olefin are sequentially added to a hydrocarbon solvent
(such as benzene, toluene, xylene, pentane and hexane) and stirred
at a temperature of 50.degree. C. or lower for about 24 hours, and
after completing the reaction, and the catalyst is deactivated with
hydrochloric acid, followed by distilling the product in vacuum,
and a dimer of the .alpha.-olefin can be obtained with high purity
and high yield.
In the case where a metallocene complex catalyst containing a
metallocene complex and alkylaluminoxane, preferably
methylaluminoxane, is used, the charging ratio (molar ratio) of the
complex metal and Al of the alkylaluminoxane is important. In the
case where the ratio is in a range of from 1.0 to 0.01, the yield
on dimerization is good, and the vinylidene olefin content in the
dimer is increased. In the case where it is 1.0 or less, the yield
on dimerization per unit complex is increased, and in the case
where it is 0.01 or more, a trimer and higher oligomers are
suppressed from being formed, whereby the yield of the dimer is
improved. The reaction temperature is about from room temperature
to 100.degree. C. In the case where it is room temperature or
higher, the dimerization reaction is accelerated, and in the case
where it is 100.degree. C. or lower, the complex is suppressed from
being deactivated, whereby the yield of the dimer is improved. The
charging ratio (proportion) of the metallocene complex with respect
to the .alpha.-olefin is generally about from 1 to 1,000 .mu.mol of
the metallocene complex per 1 mol of the .alpha.-olefin. In the
case where the amount of the metallocene complex is 1 .mu.mol or
more, the dimerization reaction is accelerated, and in the case
where it is 1,000 .mu.mol or less, heat generation is suppressed to
facilitate control of the reaction.
A dimer containing the vinylidene olefin at a high concentration
can also be produced in the case of using the metallocene complex
catalyst containing a metallocene complex and a borate. With the
metallocene complex catalyst containing a metallocene complex and a
borate, an organoaluminum compound, preferably trialkylaluminum,
and more preferably triisobutylaluminum, is preferably used in
combination.
The using amount of the borate is preferably in a range of from a
substantially equal amount to five times the amount of the complex
metal in terms of molar number. The addition amount of the
organoaluminum is not particularly limited, and is preferably at
least such a molar number that is capable of being reacted with
impurities, such as water, hydroxyl groups and amines coexisting in
the reaction system. The reaction temperature is about from room
temperature to 150.degree. C., and the optimum temperature is at
around 100.degree. C. The addition ratio of the metallocene complex
to the .alpha.-olefin is the same as that in the case using the
metallocene complex catalyst containing a metallocene complex and
methylaluminoxane described above.
The 2-position branched epoxide (2,2-dialkylepoxide) represented by
the formula (1) can be obtained by epoxidizing the vinylidene
olefin obtained by the dimerization reaction. The epoxidation
reaction can be carried out by using a peroxide. Examples of the
peroxide include hydrogen peroxide, an organic peracid, a diacyl
peroxide, a ketone peroxide, a hydroperoxide, a dialkyl peroxide, a
peroxyketal, an alkyl perester and a percarbonate. These may be
used solely or as a mixture of two or more of them. The charging
molar ratio of the peroxide and the dimer is preferably
peroxide/dimer .gtoreq.1, and more preferably
100.gtoreq.peroxide/dimer .gtoreq.1.
In the case where hydrogen peroxide is used as the peroxide, it can
be obtained, for example, through the following reaction. A
hydrogen peroxide aqueous solution (hydrogen peroxide content:
about 20 to 80% by mass) and a small amount of an acid, such as
sulfuric acid and formic acid, are mixed with the vinylidene
olefin, and then stirred generally at from 0 to 100.degree. C. for
from 1 to 50 hours. The resulting reaction product is poured into
water, and an organic layer is washed with water. A hydrogen
peroxide aqueous solution (hydrogen peroxide content: about 20 to
80% by mass) and a small amount of an acid, such as sulfuric acid
and formic acid, are then again mixed with the organic layer, and
the stirring operation is continued at from 0 to 100.degree. C. for
from 1 to 50 hours. The organic layer is washed with water and then
dried, and the hydrocarbon solvent is distilled off under reduced
pressure to obtain the 2-position branched epoxide represented by
the general formula (1) as a concentrated liquid.
The 2-position branched epoxide thus obtained is used as a raw
material, and the epoxide is subjected to acid rearrangement
reaction using a polyacid of a metallic oxoacid as a catalyst,
whereby the aldehyde with a 2-position branched long-chain alkyl
represented by the general formula (2) can be obtained.
An oxoacid includes an oxoacid containing a non-metallic atom and a
metallic oxoacid, and the oxoacid containing a non-metallic atom
includes sulfuric acid, sulfurous acid, phosphoric acid,
phosphorous acid, hypochlorous acid, chloric acid, perchloric acid,
arsenic acid and the like. The metallic oxoacid in the present
invention is an acid having a polyhedral structure, such as a
tetrahedron, a trigonal pyramid and a octahedron, formed by tetra-
to hexa-coordination of a typical metal or a transitional metal
with oxygen, and specific examples thereof include silicic acid,
aluminic acid, tungstic acid, molybdic acid and vanadic acid. In
the present invention, a polyacid of an oxoacid containing a
transition metal, such as tungstic acid, molybdic acid and vanadic
acid, is preferably used.
As a polyacid, such compounds as pyrophosphoric acid and
polyphosphoric acid formed by condensation of phosphoric acid have
been known and used widely, and the polyacid of a metallic oxoacid
used in the present invention is such a polynuclear complex that
contains, as a basic unit, a polyhedron, such as a tetrahedron, a
trigonal pyramid and a octahedron, formed by tetra- to
hexa-coordination of a typical metal or a transitional metal with
oxygen, and is formed by polycondensation of the polyhedrons with
edges and apexes thereof being shared, like wooden building blocks.
The polynuclear complex is generally referred to as a polyacid, and
a Keggin type (PW.sub.12O.sub.40).sup.3- and a Dawson type
(P.sub.2W.sub.18O.sub.62).sup.n- are known as typical examples. A
polyacid constituted only by a metallic atom and an oxygen atom is
an isopolyacid. A heteropolyacid is a polyacid that is constituted
by other metals or elements in addition to a typical metal and a
transition metal.
In the present invention, a polyacid of tungstic acid, molybdic
acid or vanadic acid is preferred as an isopolyacid, and a polyacid
of tungstic acid, molybdic acid or vanadic acid with phosphoric
acid, silicic acid or boric acid is preferred as a heteropolyacid.
Examples of the heteropolyacid include silicotungstic acid and
phosphomolybdic acid. In the present invention, particularly,
silicotungstic acid, phosphomolybdic acid and the like are
preferably used as a heteropolyacid.
In the present invention, the polyacid of a metallic oxoacid may be
supported on a carrier. Examples of the carrier that can be used
include zirconia, silica, titania and alumina. The polyacid of a
metallic oxoacid can be supported according to a known method.
An epoxy compound generally undergoes polymerization easily to
provide a polyalkylene ether A 1,2-epoxide of a long-chain
.alpha.-olefin similarly undergoes polymerization. However,
ring-opening reaction of an epoxide using a solvent capable of
being reacted with an epoxide brings about solvation. In the case
where water is used as a solvent, a 1,2-diol is by-produced.
Accordingly, when an epoxide is reacted by using an ordinary acid
catalyst with no solvent, dimerization or oligomerization of the
epoxide generally proceeds.
However, when a cluster of a metallic oxoacid (oligomer condensate,
for example, a heteropolyacid or an isopolyacid) or a polymer
thereof (super-high molecular weight condensate, for example,
zeolite, silica-alumina) is used, reaction exceeding dimerization
(intermolecular reaction) of the epoxide is suppressed, and a
product of intramolecular acid rearrangement reaction of the
epoxide becomes a main product. In the case where a cluster of a
metallic oxoacid (low condensate of an oxoacid containing a
transition metal) referred to as a polyacid is used, the catalytic
activity and selectivity to a saturated aldehyde with a 2-position
branched long-chain alkyl are improved, whereby the target product
can be produced with good efficiency.
As by-products, a long-chain alkyl 2-position branched unsaturated
alcohol represented by the general formula (i), a long-chain alkyl
2-position branched 1,2-diol represented by the general formula
(ii), an epoxide dimer represented by the general formula (iii) and
the like are identified, but a 2-position branched unsaturated
alcohol, which is an acid rearrangement product having a boiling
point close to the aldehyde with a 2-position branched long-chain
alkyl represented by the general formula (2) as a target product,
is suppressed from being produced, and thus a heteropolyacid is
practically useful as the catalyst.
The charging ratio (proportion) of the polyacid of a metallic
oxoacid with respect to the vinylidene olefin represented by the
general formula (1) is generally from 0.1 to 25 mol of transition
metal atoms of the polyacid of a metallic oxoacid used per 1 mol of
the vinylidene olefin represented by the general formula (1). For
example, it is from 0.1/12 to 25/12 mol for silicotungstic acid
H.sub.4(Si(W.sub.3O.sub.10).sub.4).xH.sub.2O. In the case where the
polyacid of a metallic oxoacid is 0.1 mol or more per transition
metallic atoms, the acid rearrangement reaction is accelerated, and
in the case where it is 25 mol or less, the polyacid is dissolved
through reaction of the polyacid and the epoxide to suppress a
phenomenon of suddenly increasing the reaction rate, whereby
control of the reaction is facilitated.
The acid rearrangement reaction can be carried out at a reaction
temperature of generally about from 20 to 200.degree. C., and
preferably from 100 to 150.degree. C., for a reaction time of
generally about from 30 minutes to 4 hours, and preferably from 1
to 2 hours. The product obtained through the acid rearrangement
reaction can be easily purified by such a method as
distillation.
EXAMPLES
The present invention is described in more detail with reference to
examples, but the invention is not limited by the examples.
Production Example 1
(1) Dimerization Reaction of Linear .alpha.-Olefin
3.0 kg of 1-decene, zirconocene dichloride (metallocene complex,
0.9 g, 3 mmol) and methylaluminoxane (produced by Albemarle Corp.,
8 mmol (in terms of Al)) were placed sequentially in a three-neck
flask having an internal capacity of 5 L having been substituted
with nitrogen, and stirred at room temperature (ca. 20.degree. C.).
The reaction solution was changed from yellow to reddish brown.
After reacting for 48 hours, 30 mL of methanol was added thereto to
terminate the reaction, and 300 mL of a hydrochloric acid aqueous
solution was added to the reaction solution, followed by washing
the organic layer. The organic layer was then distilled in vacuum
to obtain 2.5 kg of a distillate fraction (decene dimer) having a
boiling point of 120 to 125.degree. C. at 26.6 Pa (0.2 Torr) Gas
chromatography analysis of the distillate fraction revealed that
the concentration of the decene dimer was 99% by mass, and the
proportion of the vinylidene olefin (2-octyl-1-dodecene) in the
dimer was 97% by mass.
(2) Epoxidation Reaction of Vinylidene Olefin
300 g of the decene dimer prepared in the item (1) and mL of
toluene were placed in a three-neck flask having an internal
capacity of 2 L, and were mixed. While maintaining the temperature
of the mixture to 70.degree. C., 150 g of hydrogen peroxide aqueous
solution having a concentration of 30% by mass, g of concentrated
sulfuric acid and 20 g of formic acid were added thereto. After
stirring the mixture at that temperature for 1.5 hours, the
reaction mixture was poured into mL of water, followed by washing
the organic layer. The organic layer was placed again in the flask,
and 150 g of a hydrogen peroxide aqueous solution having a
concentration of 30% by mass, 0.5 g of concentrated sulfuric acid
and 20 g of formic acid were added thereto. After continuing the
stirring operation at 70.degree. C. for 1.5 hours, the mixture was
fractionated to obtain an organic layer, which was washed with
water and then dried. Toluene as a solvent was distilled off under
reduced pressure to obtain 302 g of a concentrated liquid. Analysis
of the concentrated liquid by .sup.1H-NMR and .sup.13C-NMR
confirmed that the concentrated liquid was
2-octyl-1,2-epoxydodecane with the content thereof being 99%.
Example 1
(1) Acid Rearrangement Reaction with Molybdophosphoric Acid
(Heteropoly Acid)
0.5 g of 12 molybdo(IV)phosphoric acid n hydrate (produced by Kanto
Chemical Co., Inc.) was charged in a flask having an internal
capacity of 300 mL, and while heating the flask to 170.degree. C.,
water vaporized from the hydrate was removed at a vacuum degree of
133 Pa (1 Torr). The crystals were changed from pale yellow to
bluish purple. 100 g (338 mmol) of 2-octyl-1,2-epoxydodecane
produced in Production Example 1 was added to 12 molybdo(IV)
phosphoric acid having been dehydrated, and stirred at room
temperature (25.degree. C.). Heat was generated after lapsing about
10 minutes, and the internal temperature was returned to room
temperature after lapsing 30 minutes. The reaction mixture was then
heated over an oil bath at 100.degree. C., and heated at that
temperature for 2 hours. After cooling, the reaction product was
diluted with 100 mL of toluene, and then washed with water to
obtain water washing product. Gas chromatography analysis of the
product revealed that the formation proportions were 92% by mass
for 2-octyl-1-dodecanal, 5% by mass for 1,3-dioxolane as a
dimerization product of the epoxide, and 3% by mass for light
hydrocarbon compounds. The results are shown in Table 1.
(2) Separation and Purification of 2-Octyl-1-Dodecanal
Toluene was distilled off from the water washing product of the
item (1) with an evaporator to obtain 96 g of a concentrated
product. The concentrated product was then placed in a vacuum
distillation apparatus and distilled at a vacuum degree of 33.3 Pa
(0.25 Torr) over an oil bath at 170.degree. C. A distillation
fraction of a distillation temperature of from 139 to 145.degree.
C. was fractionated to obtain 82 g (277 mmol) of
2-octyl-1-dodecanal. Accordingly, the yield of 2-octyl-1-dodecanal
was 82%, and the purity thereof was 97.5%, which revealed that
synthesis was attained with high yield and high purity.
(3) Structure of 2-Octyl-1-Dodecanal
The structure of 2-octyl-1-dodecanal purified in the item (2) was
identified by .sup.1H-NMR and .sup.13C-NMR. Upon analysis, the
carbon atoms of 2-octyl-1-dodecanal were attached with symbols.
As a result of analysis, in .sup.1H-NMR, in which the peak of TMS
(tetramethylsilane) was designated as 0 ppm, and hydrogen attached
to carbon(s) was expressed as (1)H, the attributes of the protons
were (1)H 9.55 ppm, (2)H 2.22 ppm, (3)H 1.61 ppm, 1.41 ppm,
(4)H-(8)H 1.26 ppm and (9)H 0.88 ppm.
FIG. 1 shows the .sup.1H-NMR spectrum.
In .sup.13C-NMR, in which the center peak of CDCl.sub.3 was
designated as 76.91 ppm, the attributes of the carbon were (1)
205.4 ppm, (2) 51.9 ppm, (3) 28.8 ppm, (4) 27.0 ppm, (5) 29.6 ppm,
(6) 29.5-29.1 ppm, (7) 31.8 ppm, (8) 22.5 ppm and (9) 13.9 ppm.
FIG. 2 shows the .sup.13C-NMR spectrum. FIG. 2(B) is an enlarged
figure of the part shown by a symbol A in FIG. 2(A).
In the .sup.13C-NMR spectrum, the intensity ratio of the carbon
peaks of (2) and (3) is 1/2, which evidences that there are two
atoms of carbon(3) per carbon (2), i.e., a branch of carbon(3)
occurs at carbon(2).
FIG. 3 shows the homonuclear shift correlation (2D-COSY) spectrum.
In FIG. 3, correlation signals of (2)H and (I)H, and (2)H and (3)H
are observed (shown by arrows in FIG. 3), which indicate the
structure. That is, (2)H is positioned between (1)H and (3)H.
Furthermore, (1)H is positioned at a low magnetic field, which
indicates aldehyde hydrogen.
Example 2
Acid Rearrangement Reaction with Silicotungstic Acid (Heteropoly
Acid)
0.05 g of silicotungstic acid hydrate (produced by Kanto Chemical
Co., Inc.) was charged in a flask having an internal capacity of
300 mL, and while heating the flask to 170.degree. C., water
vaporized from the hydrate was removed at a vacuum degree of 133 Pa
(1 Torr). The crystals were changed from white to gray. 100 g (338
mmol) of 2-octyl-1,2-epoxydodecane produced in Production Example 1
was added to silicotungstic acid having been dehydrated, and
stirred at room temperature (25.degree. C.). Heat was vigorously
generated after lapsing several minutes, and the internal
temperature was returned to around room temperature after lapsing 1
hour. The reaction mixture was then heated over an oil bath at
100.degree. C., and heated at that temperature for 1 hour. After
cooling, the reaction product was diluted with 100 mL of toluene,
and then washed with water to obtain concentrated reaction product.
The resulting concentrated reaction product was 96 g. Gas
chromatography analysis of the concentrated reaction product
revealed that the formation proportions were 72% by mass for
2-octyl-1-dodecanal, 9% by mass for a long-chain alkyl 2-position
branched unsaturated alcohol, 4% by mass for a long-chain alkyl
2-position branched 1,2-diol, 9% by mass for 1,3-dioxolane, and 6%
by mass for light hydrocarbon compounds. The results are shown in
Table 1.
Example 3
Acid Rearrangement Reaction with Molybdic Acid (Isopoly Acid)
0.1 g of hexaammonium heptamolybdate tetrahydrate (produced by
Kanto Chemical Co., Inc.) was charged in a Schlenk flask having an
internal capacity of 100 mtL, to which 0.1 mL of concentrated
sulfuric acid having a concentration of 98% by mass was added, and
the mixture was stirred over an oil bath at 80.degree. C. for 30
minutes. 20 g of 2-octyl-1,2-epoxydodecane was added to the
resulting slurry under stirring, and the mixture was stirred
continuously at 80.degree. C. for 2 hours. After cooling, the
reaction product was diluted with 20 mL of toluene, and then washed
with water. Analysis of the reaction product revealed that the
formation proportions were 85% by mass for 2-octyl-1-dodecanal, 3%
by mass for a long-chain alkyl 2-position branched unsaturated
alcohol, 1% by mass for a long-chain alkyl 2-position branched
1,2-diol, 8% by mass for 1,3-dioxolane, and 3% by mass for light
hydrocarbon compounds. The results are shown in Table 1.
Example 4
Acid Rearrangement Reaction with Molybdic Acid Supported on
Zirconia
9 g of zirconium oxide powder (Zirconia, 3N, produced by Kanto
Chemical Co., Inc.), 1 g of phosphomolybdic acid and 50 mL of
distilled water were placed on a porcelain dish and then evaporated
to dryness under stirring over a water bath. The powder thus
obtained was fired in a muffle furnace at 1,073.degree. C. for 2
hours to prepare a molybdic acid/zirconia catalyst. 0.1 g of the
powder thus prepared was charged in a Schlenk flask having an
internal capacity of 100 mL, to which 20 g of
2-octyl-1,2-epoxydodecane was added, followed by continuing the
stirring operation at 100.degree. C. for 2 hours. After cooling,
the reaction mixture was diluted with 20 mL of toluene, and the
reaction product was filtered and washed with water. Gas
chromatography analysis of the reaction product revealed that the
formation proportions were 87% by mass for 2-octyl-1-dodecanal, 8%
by mass for 1,3-dioxolane, and 5% by mass for light hydrocarbon
compounds. The results are shown in Table 1.
Example 5
Acid Rearrangement Reaction with Tungstic Acid Supported on
Silica)
0.1 g of 10% by mass silicotungstic acid/silica (N.E. Chemcat
Corp.) was charged in a two-neck flask having an internal capacity
of 100 mL, to which 20 g of 2-octyl-1,2-epoxydodecane was added,
followed by stirring at room temperature for 30 minutes. The
reaction mixture was then further stirred over an oil bath at
100.degree. C. for 1 hour. After cooling, the reaction mixture was
diluted with 20 mL of toluene, and the reaction product was
filtered and washed with water. Gas chromatography analysis of the
reaction product revealed that the formation proportions were 77%
by mass for 2-octyl-1-dodecanal, 6% by mass for a long-chain alkyl
2-position branched unsaturated alcohol, 2% by mass for a
long-chain alkyl 2-position branched 1,2-diol, 8% by mass for
1,3-dioxolane, and 7% by mass for light hydrocarbon compounds. The
results are shown in Table 1.
Comparative Example 1
Acid Rearrangement Reaction with Concentrated Sulfuric Acid
1.2 mL of a sulfuric acid aqueous solution having a concentration
of 50% by mass and 20 g (67.6 mmol) of 2-octyl-1,2-epoxydodecane
were placed in a Schlenk flask having an internal capacity of 100
mL, and continuously stirred at 100.degree. C. for 2 hours. After
cooling, the reaction mixture was diluted with 20 mL of toluene,
and the reaction product was washed with an alkali aqueous
solution. The washed solution was dried with Kyoward 500 (produced
by Kyowa Chemical Industry Co., Ltd.) and filtered to obtain 14 g
of a concentrated product Gas chromatography analysis of the
concentrated product revealed that the formation proportions were
28% by mass for 2-octyl-1-dodecanal, 14% by mass for a long-chain
alkyl 2-position branched unsaturated alcohol, 3% by mass for a
long-chain alkyl 2-position branched 1,2-diol, 51% by mass for
1,3-dioxolane, and 4% by mass for light hydrocarbon compounds. The
results are shown in Table 1.
Comparative Example 2
Acid Rearrangement Reaction with Phosphoric Acid
1.2 mL of 85% by mass phosphoric acid and 20 g of
2-octyl-1,2-epoxydodecane were placed in a Schlenk flask having an
internal capacity of 100 mL, and continuously stirred at
100.degree. C. for 2 hours. After cooling, the reaction mixture was
diluted with 20 mL of toluene, and the reaction product was washed
with an alkali aqueous solution. The washed solution was dried with
Kyoward 500 (produced by Kyowa Chemical Industry Co., Ltd.) and
filtered to obtain 15 g of a concentrated product. Gas
chromatography analysis of the concentrated product revealed that
the formation proportions were 23% by mass for 2-octyl-1-dodecanal,
16% by mass for a long-chain alkyl 2-position branched unsaturated
alcohol, 4% by mass for a long-chain alkyl 2-position branched
1,2-diol, 40% by mass for 1,3-dioxolane, and 17% by mass for light
hydrocarbon compounds. The results are shown in Table 1.
TABLE-US-00001 TABLE 1 Charged mass Target By-product By-product
By-product By-product ratio product 1 2 3 4 Catalyst
catalyst/epoxide (% by mass) (% by mass) (% by mass) (% by mass) (%
by mass) Example 1 phosphomolybdic acid 0.5 g/100 g 92 0 0 5 3
Example 2 silicotungstic acid 0.05 g/100 g 72 9 4 9 6 Example 3
molybdic acid 0.1 g/20 g 85 3 1 8 3 Example 4 molybdic acid 0.1
g/20 g 87 0 0 8 5 supported on zirconia Example 5 tungstic acid 0.1
g/20 g 77 6 2 8 7 supported on silica Comparative 50% sulfucic acid
1.2 mL/20 g 28 14 3 51 4 example 1 aqueous solution Comparative 85%
phosphoric acid 1.2 mL/20 g 23 16 4 40 17 Example 2 (Note) Target
product: 2-octyl-1-dodecanal By-product 1: long-chain alkyl
2-position branched unsaturated alcohol By-product 2: long-chain
alkyl 2-position branched 1,2-diol By-product 3: 1,3-dioxolane
(dimer of epoxide) By-product 4: light hydrocarbon confounds
The structure of the by-product 3 was determined as 1,3-dioxolane
structure since an antisymmetric stretching .nu..sub.R--O--R=1,115
cm.sup.-1 showing characteristic absorption of ether appeared in
the infrared absorption spectrum, and the parent peak 591
(C.sub.40H.sub.80O.sub.2=592) was obtained in the mass spectrum.
The structure was also supported by analysis by .sup.13C-NMR and
.sup.1H-NMR.
INDUSTRIAL APPLICABILITY
An aldehyde with a 2-position branched long-chain alkyl produced by
the production process of the present invention is suitable for an
intermediate raw material used in production of a branched alcohol,
a branched fatty acid, an aliphatic amine and the like, a resin raw
material, such as 1,3-alkanediol and a bisphenol derivative, and a
raw material of a functional chemical utilizing a Schiff base and
the like.
* * * * *